CN111575491B - Resource comprehensive utilization method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt - Google Patents
Resource comprehensive utilization method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt Download PDFInfo
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Abstract
The invention discloses a resource comprehensive utilization method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenate, which comprises the steps of carrying out alkaline leaching on the cobalt-nickel slag purified by the zinc hydrometallurgy arsenate, and filtering to obtain an alkaline leaching solution and alkaline leaching slag; cooling and crystallizing the alkaline leaching solution to obtain sodium arsenate, dissolving the sodium arsenate with water, adjusting pH to 2-4, and introducing SO2Reducing to obtain a sodium arsenite solution; carrying out second-stage leaching on the alkaline leaching residue, wherein the first-stage low-acid leaching is carried out, and the second-stage high-acid leaching is carried out; adding copper powder into the low-acid leaching solution, removing arsenic from the copper powder, and filtering to obtain arsenic-removed solution and arsenic-removed slag; performing potential-controlled copper precipitation on the arsenic-removing solution, and filtering to obtain a copper precipitation solution and copper powder; and adding sodium hypochlorite into the solution after copper removal for cobalt precipitation by oxidation. The recovery of the cobalt-nickel slag has the advantages of reasonable process, low separation cost, environmental protection and the like.
Description
Technical Field
The invention relates to the field of resource utilization of cobalt-nickel slag purified by zinc hydrometallurgy arsenate, in particular to a resource comprehensive utilization method of cobalt-nickel slag purified by zinc hydrometallurgy arsenate.
Background
In the process of zinc hydrometallurgy at home and abroad, zinc powder and arsenic trioxide are adopted for purification (arsenic salt purification for short) to remove cobalt, so that the zinc powder consumption is low, the purification effect is good, and the produced copper slag and cobalt-nickel slag have high valuable metal enrichment degree. Arsenic salt is adopted to purify zinc sulfate solution in a certain wet zinc-smelting plant at home to remove cobalt, and the annual cobalt-nickel slag is 1500-1800 tons, wherein the slag contains valuable metals of Cu42-53%, Co1.5-5.0%, Zn8-13%, and contains As 8-15%.
The cobalt-nickel slag has high contents of valuable elements such as copper, cobalt, zinc and arsenic, contains a certain amount of lead and silver, and has high recovery value. However, arsenic and elements such as copper, cobalt and nickel in the slag exist in an alloy form, so that the stability is high, the components are complex, the treatment difficulty is relatively high, and the copper in the cobalt-nickel slag is recovered after some factories do not treat or only simply treat the copper, so that the resource waste is caused, and the environmental pollution is easily caused. If the raw copper is sent to a copper blast furnace to recover copper, valuable metals such As zinc, cobalt and the like are not recovered, and As enters smoke or a small part of As enters crude copper or slag, so that smoke dust is difficult to recover, the As contained in the crude copper also affects electrolysis, and meanwhile, the zinc, the cobalt, the arsenic and the like entering the slag increase the slag amount, the copper smelting energy consumption increases, and the unit production cost increases.
A process for treating the purified slag for removing cobalt from antimonate in No. 9 of resource regeneration 2010 comprises the following steps: valuable metals such as zinc, cadmium, cobalt and the like are leached in an acid manner and enter a solution, copper is controlled to enter slag, iron is removed from a leaching solution through oxidation, copper is removed through zinc powder, cobalt is precipitated, and cobalt precipitation slag is subjected to acid washing and impurity removal and then is roasted to obtain cobaltosic oxide. The disadvantage of this process is that the nickel and zinc in the slag are not efficiently recovered. The 32 nd No. 4 of the university newspaper of Zhongnan, 2001, proposes a process for treating wet-process zinc smelting antimonate purified cobalt slag by an ammonia-ammonium sulfate system. The method can directly extract cobalt or cobalt salt and prepare active zinc powder at the same time, but the process adopts ammonium-ammonia water solution as a leaching agent, and the operation environment is relatively severe. The paper in the monograph of the research and treatise on the localization of zinc pressure leaching process and the direct reduction of liquid lead slag reports the pyrogenic process and wet process combined extraction process of valuable elements in cobalt-nickel slag produced by arsenic salt purification process. The second-stage leaching residue is selectively leached with zinc, and the leached residue is roasted to open the arsenic and convert valuable metals such as copper, cobalt, nickel and the like into oxides which are easy to leach by acid. After acid leaching of the roasting slag, removing copper by iron powder replacement to separate copper from cobalt and nickel. The process obviously has the problem of overhigh iron content in the solution after copper removal.
CN 102534235A discloses a method for recovering valuable metals from cobalt-nickel slag purified by zinc and arsenic salt hydrometallurgy, which comprises the following steps: selective leaching of sulfuric acid, calcination, secondary leaching of sulfuric acid, arsenic copper precipitation and cobalt nickel precipitation, so that valuable metals such as zinc, copper, cobalt and nickel in cobalt nickel slag can be separated and recovered respectively. CN 102965499B discloses a method for extracting valuable elements from arsenic salt purification slag in zinc hydrometallurgy. The method adopts a full-wet process to treat the arsenic salt purification slag of the zinc hydrometallurgy, and recovers cobalt and nickel by selective zinc leaching, oxidation leaching of lead, neutralization arsenic and copper precipitation and precipitation; and (4) carrying out alkaline leaching on the arsenic-precipitated copper slag obtained by neutralizing and precipitating arsenic to separate copper and arsenic. CN 105567999B discloses a method for recovering valuable metals from cobalt-nickel slag purified by zinc and arsenic salt hydrometallurgy, which comprises the following steps: leaching zinc electrolysis waste liquid, roasting, secondary acid leaching of the zinc electrolysis waste liquid, and oxidizing and precipitating cobalt by potassium permanganate, thereby realizing the recovery of valuable metals such as Zn, Co, Ni and the like. These three methods are similar, and all have the problem of waste water discharge, and generate poisonous gas arsenic hydride in the selective zinc dipping step.
Therefore, how to find a method for effectively separating valuable metals from cobalt-nickel slag and respectively recovering the valuable metals is a problem to be further explored.
Disclosure of Invention
The invention aims to provide a comprehensive resource utilization method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenate, which has the characteristics of environmental protection, is simple and feasible, and has the advantages that valuable elements of arsenic, zinc, copper, cobalt, silver and lead in the cobalt-nickel slag are all recovered, arsenic is returned to an arsenate purification system for reuse in the form of sodium arsenite, and the recovery rate reaches 95 percent; the zinc recovery system recovers the zinc; the copper is subjected to potential-controlled copper precipitation to obtain high-purity copper powder, and the recovery rate is over 98 percent; the cobalt is separated and recovered in the form of cobaltosic oxide, the recovery rate exceeds 92 percent, and lead and silver are enriched in the second-stage acid leaching residue. The technology of the invention has no special equipment requirement and no three wastes, and belongs to a green and environment-friendly wet smelting process.
The technical scheme of the invention is as follows:
a resource comprehensive utilization method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt is characterized by comprising the following steps:
A. high-pressure alkaline arsenic leaching: leaching the cobalt-nickel slag (hereinafter referred to as cobalt-nickel slag) purified by the zinc-arsenic salt hydrometallurgy at the alkali concentration of 3.8-5.2mol/L and the leaching temperature of 125-;
B. and (3) arsenic reduction: cooling and crystallizing the alkaline leaching solution obtained in the step A to obtain sodium arsenate crystals, dissolving the sodium arsenate crystals by using water to obtain a sodium arsenate solution, adjusting the pH value of the sodium arsenate solution to 2-4, and introducing SO2Reducing to obtain a sodium arsenite solution; wherein the reduction time is 1.5-3.0h, SO2The dosage is SO2The molar ratio of the arsenic in the sodium arsenate solution to the arsenic (2.05-2.15) is 1;
C. acid leaching: b, performing secondary leaching on the alkaline leaching residue obtained in the step A, performing primary low-acid leaching, wherein the sulfuric acid concentration of a low-acid leaching solution is 15-25 g/L, and the end point pH =1.5-2.8, so as to obtain a low-acid leaching solution, the Cu ion concentration of the low-acid leaching solution is 80-95g/L, the low-acid leaching residue is subjected to secondary high-acid leaching, and the sulfuric acid concentration of the high-acid leaching solution is 60-90 g/L;
D. purifying and removing arsenic: c, performing copper powder arsenic removal on the low-acid leaching solution obtained in the step C at the temperature of 82-88 ℃ for 3-5h, wherein the using amount of copper powder is 3-5g/L, and filtering to obtain arsenic removal liquid and arsenic removal slag;
E. controlling potential to deposit copper: d, carrying out potential-controlled copper deposition on the arsenic-removing liquid obtained in the step D, wherein the copper deposition temperature is 55-65 ℃, the copper deposition time is 60-90min, the end point pH =3.2-4.5, and the end point potential is 80-100 mv, and filtering to obtain a copper deposition liquid and copper powder;
F. and (3) oxidizing and precipitating cobalt: and D, adding sodium hypochlorite into the copper-removed liquid obtained in the step E for carrying out oxidation cobalt precipitation at the temperature of 75-85 ℃ for 60-90min, wherein the end point pH = 3.5-5.0.
As a further improvement of the invention, the liquid-solid ratio in the step A is (4-6) to 1, the oxygen partial pressure is 2.6-3.0MPa, and the introduced oxygen is pure oxygen.
As a further improvement of the invention, sulfuric acid is used for adjusting the acidity of the solution in the step B, arsenic trioxide crystals which are saturated and separated out in the reduction process are dissolved by using a sodium hydroxide solution to obtain a sodium arsenite solution containing 100-130g/L of As, and zinc is returned to the wet method for refining zinc for purifying arsenic salt to remove cobalt.
As a further improvement of the invention, the leaching agent in the step C is a sulfuric acid solution, the first stage leaching is low acid leaching, the leaching temperature is 55-65 ℃, and the leaching time is 60-90 min; the second stage leaching is high-acid leaching, the liquid-solid ratio (namely the mass percentage of the leaching agent to the first stage leaching residue) of leaching is (8-12): 1, the leaching temperature is 80-85 ℃, the leaching time is 3-5h, the sulfuric acid content at the end of leaching is 15-30g/L, and 10-20mL of hydrogen peroxide is added into each liter of solution when the end point is approached.
As a further improvement of the invention, the copper powder in the step D is activated copper powder, and the particle size is controlled to be 180-260 meshes.
As a further improvement of the invention, the activated copper powder in the step D is obtained by further activating fresh sponge copper powder obtained by controlling the potential for copper deposition in the next step.
As a further improvement of the invention, the copper-deposited zinc powder in the step E is 0.98-1.0 times of the theoretical amount required for replacing copper (the theoretical amount is that 1 mole of zinc powder is required for replacing 1 mole of copper ions); the quality requirements of the used zinc powder are as follows: zn is more than or equal to 99.9 percent, and the granularity of the zinc powder is 0.25-0.09 mm; the copper content in the solution after copper precipitation is 0.23-0.32 g/L.
As a further improvement of the invention, copper powder obtained by copper deposition in the controlled potential in the step E is firstly subjected to acid washing by a sulfuric acid solution with the sulfuric acid content of 20-30g/L, the acid washing temperature is 50-60 ℃, the time is 60-90 minutes, and the liquid-solid ratio (5-8) is 1.
As a further improvement of the method, the copper powder after acid washing in the step E is washed by deionized water for 2 times, the washing temperature is 45-55 ℃, the washing time is 30-45min, the liquid-solid ratio is (5-8): 1, and the copper powder obtained by filtering is subjected to vacuum drying treatment.
As a further improvement of the invention, the copper powder dried in the step E is ball-milled in protective conditions such as nitrogen or argon or in kerosene to obtain the product of superfine copper powder.
As a further improvement of the invention, the free alkali in the sodium hypochlorite in the step F is between 0.1 and 0.5 percent, the effective rate is between 5 and 11 percent, and the required amount of the sodium hypochlorite is 12 to 15 times of the theoretical amount of the divalent cobalt oxide to the trivalent cobalt.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the cobalt-nickel slag is subjected to high-pressure alkaline leaching and the alkaline leaching slag is subjected to first-stage low-acid leaching to obtain a low-acid leaching solution, and a purification arsenic removal process is adopted, so that the grade of copper powder obtained by subsequent potential-controlled copper precipitation is ensured, and the generation of toxic gas arsine is avoided; the sodium arsenate solution obtained by high-pressure alkaline leaching adopts an alkaline leaching reduction technology, and the generated arsenite is used for purifying and removing cobalt from zinc arsenate in a hydrometallurgy process, so that the cyclic utilization of arsenic is formed in the system, and the purposes of environmental protection and comprehensive recovery of resources are achieved; through high-pressure alkaline leaching and second-stage acid leaching, lead and silver in acid leaching residues are enriched by 30-40 times compared with cobalt and nickel residues, and the acid leaching residues can be used as raw materials for recovering lead and silver or can be sold; meanwhile, the copper powder recovered by the potential control technology is processed to obtain superfine copper powder; the cobalt is recovered by precipitation as cobaltosic oxide. Wherein the recovery rates of arsenic, copper, zinc, cobalt, lead and silver are respectively 95%, 98%, 96%, 92%, 98.5% and 98.5%. The method provided by the invention can separate and recover valuable metals arsenic, copper, zinc, cobalt, lead and silver in the cobalt-nickel slag respectively, and has the advantages of simple process and low production cost. The method provided by the invention eliminates the pollution influence of cobalt-nickel slag accumulation on the environment or the risk of arsenic metal pollutants caused by copper blast furnace treatment in the prior art, forms the cyclic utilization of arsenic in the system, and really realizes the comprehensive recovery of valuable resources in the cobalt-nickel slag.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It is to be understood that the specific examples described herein are merely illustrative of the present invention and are not intended to limit the present invention, and the present invention encompasses other embodiments and modifications thereof within the scope of the technical spirit thereof.
The embodiment of the invention provides a resource comprehensive utilization method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenate, and please refer to fig. 1.
The invention is further illustrated by the following specific examples.
Example 1
A. High-pressure alkaline arsenic leaching: the mass percentage concentration is as follows: the method comprises the steps of leaching cobalt-nickel slag containing 12.37% of Zns, 55.45% of Cus, 3.41% of Cos, 13.28% of Ass, 3.24% of Pbs and 0.017% of Ags under the condition that the alkali concentration is 5.2mol/L, wherein the leaching temperature is 125 ℃, the liquid-solid ratio is 4:1, introducing pure oxygen with the oxygen partial pressure of 2.6MPa, leaching for 3 hours, and filtering to obtain alkali leaching liquid and alkali leaching slag.
B. And (3) arsenic reduction: cooling and crystallizing the alkaline leaching solution obtained in the step A to obtain sodium arsenate, dissolving the sodium arsenate crystal by using water to obtain a sodium arsenate solution, adjusting the pH value of the sodium arsenate solution to 2, and then adding SO2SO is introduced into the sodium arsenate solution at a molar ratio of 2.05:12Carrying out reduction reaction for 3.0h to obtain a sodium arsenite solution; the arsenic trioxide crystals which are saturated and separated out in the reduction process are dissolved into a sodium arsenite solution with the concentration of As 130g/L by using a sodium hydroxide solution, and the solution is returned to the arsenic salt purification process in the zinc hydrometallurgy to be used As an arsenic raw material.
C. Acid leaching: b, carrying out secondary leaching on the alkaline leaching residue obtained in the step A, wherein the temperature of the first-stage low-acid leaching is 65 ℃, the leaching time is 60 minutes, and the pH of the low-acid leaching control end point is =1.5, so that a low-acid leaching solution with the Cu ion concentration of 95g/L is obtained; and (3) carrying out second-stage high-acid leaching on the low-acid leaching residue, wherein the liquid-solid ratio is 12:1, the temperature is 85 ℃, the time is 3 hours, 10mL of hydrogen peroxide is added into each liter of solution when the end point is approached, and the acidity of the high-acid leaching solution is 30 g/L.
D. Purifying and removing arsenic: and D, performing copper powder arsenic removal on the low-acid leaching solution obtained in the step C at the temperature of 82 ℃ for 5 hours, controlling the using amount of activated copper powder to be 3g/L and the granularity to be 260 meshes, and filtering to obtain arsenic removal liquid and arsenic removal slag.
E. Controlling potential to deposit copper: d, carrying out potential-controlled copper deposition on the arsenic-removing solution obtained in the step D, wherein copper deposition zinc powder is 1.0 time of the theoretical amount required for copper replacement, the temperature is 55 ℃, the time is 60 minutes, the end point pH =3.2, the end point potential is 100mv, and the copper content in the copper-deposited solution is 0.23 g/L; the copper powder obtained by filtering is firstly pickled by sulfuric acid solution with the sulfuric acid content of 20g/L at the temperature of 60 ℃ for 60 minutes, and the liquid-solid ratio is 5: 1; washing the copper powder by deionized water for 2 times at 45 ℃ for 45 minutes at a liquid-solid ratio of 8:1, and carrying out vacuum drying treatment on the washed copper powder; and ball-milling the dried copper powder under the protection of nitrogen to obtain the superfine copper powder product.
F. And (3) oxidizing and precipitating cobalt: and E, adding sodium hypochlorite into the copper-removed solution obtained in the step E for carrying out oxidation cobalt precipitation, wherein the amount of the sodium hypochlorite is 15 times of the theoretical amount of oxidizing divalent cobalt into trivalent cobalt, the temperature is 75 ℃, the time is 60min, and the end point pH = 5.0.
Through comprehensive recovery of cobalt-nickel slag resources, a sodium arsenite solution, superfine copper powder, high-acid leaching slag and the like are respectively obtained, and the recovery rates of arsenic, copper, zinc, cobalt, lead and silver are respectively 95.3%, 98.5%, 97%, 94%, 98.6% and 98.8%.
Example 2
A. High-pressure alkaline arsenic leaching: the mass percentage concentration is as follows: 12.37 percent of Zn, 55.45 percent of Cu, 3.41 percent of Co, 13.28 percent of As, 3.24 percent of Pb and 0.017 percent of Ag, introducing pure oxygen with oxygen partial pressure of 3.0MPa in the alkali concentration of 3.8mol/L, the leaching temperature of 130 ℃, the liquid-solid ratio of 4:1, leaching for 5 hours, and filtering to obtain alkali leaching solution and alkali leaching residue.
B. And (3) arsenic reduction: cooling and crystallizing the alkaline leaching solution obtained in the step A to obtain sodium arsenate, dissolving the sodium arsenate crystal with water, adjusting the pH value to 4, and then adding SO2SO is introduced into the sodium arsenate solution at a molar ratio of 2.15:12And carrying out reduction reaction for 1.5h to obtain a sodium arsenite solution, dissolving arsenic trioxide crystals which are precipitated in a saturated way in the reduction process into a sodium arsenite solution with 100g/L of As by using a sodium hydroxide solution, and returning to an arsenic salt purification process in zinc hydrometallurgy for use As an arsenic raw material.
C. Acid leaching: and B, performing secondary leaching on the alkaline leaching residue obtained in the step A, wherein the temperature of the first-stage low-acid leaching is 55 ℃, the leaching time is 90 minutes, the pH of the low-acid leaching control end point is =2.8, the Cu ion concentration of the obtained low-acid leaching solution is 80g/L, the low-acid leaching residue enters the second-stage high-acid leaching, the liquid-solid ratio is 8:1, the temperature is 80 ℃, the time is 5 hours, 20mL of hydrogen peroxide is added into each liter of solution when the end point is approached, and the acidity of the high-acid leaching solution is 15 g/L.
D. Purifying and removing arsenic: and D, performing copper powder arsenic removal on the low-acid leaching solution obtained in the step C at 88 ℃ for 3 hours, controlling the consumption of activated copper powder to be 5g/L and the granularity to be 180 meshes, and filtering to obtain arsenic removal solution and arsenic removal slag.
E. Controlling potential to deposit copper: d, carrying out potential-controlled copper deposition on the arsenic-removing liquid obtained in the step D, wherein the copper deposition zinc powder is 0.98 time of the theoretical amount required for copper replacement, the temperature is 65 ℃, the time is 90 minutes, the end point pH =4.5, the end point potential is 80mv, and the copper content in the copper deposition liquid is 0.32 g/L; the copper powder obtained by filtering is firstly pickled by sulfuric acid solution with the sulfuric acid content of 30g/L at the temperature of 50 ℃ for 90 minutes, and the liquid-solid ratio is 8: 1; washing the copper powder by deionized water for 2 times at 55 ℃ for 30 minutes at a liquid-solid ratio of 5:1, and carrying out vacuum drying treatment on the washed copper powder; and ball-milling the dried copper powder under the protection of argon to obtain the superfine copper powder product.
F. And (3) oxidizing and precipitating cobalt: and E, adding sodium hypochlorite into the copper-removed solution obtained in the step E for carrying out oxidation cobalt precipitation, wherein the amount of the sodium hypochlorite is 12 times of the theoretical amount of oxidizing divalent cobalt into trivalent cobalt, the temperature is 85 ℃, the time is 90min, and the end point pH = 3.5.
Through comprehensive recovery of cobalt-nickel slag resources, a sodium arsenite solution, superfine copper powder, high-acid leaching slag and the like are respectively obtained, and the recovery rates of arsenic, copper, zinc, cobalt, lead and silver are respectively 95.8%, 98.7%, 97.5%, 93%, 98.8% and 99.1%.
Example 3
A. High-pressure alkaline arsenic leaching: the mass percentage concentration is as follows: 12.37 percent of Zn, 55.45 percent of Cu, 3.41 percent of Co, 13.28 percent of As, 3.24 percent of Pb and 0.017 percent of Ag, introducing pure oxygen with oxygen partial pressure of 2.8MPa into cobalt-nickel slag with alkali concentration of 4.8mol/L, leaching temperature of 128 ℃, liquid-solid ratio of 5:1, leaching for 4 hours, and filtering to obtain alkali leaching solution and alkali leaching slag.
B. And (3) arsenic reduction: cooling and crystallizing the alkaline leaching solution obtained in the step A to obtain sodium arsenate, dissolving the sodium arsenate crystal with water, adjusting the pH value to 3, and introducing SO2Reducing to obtain the sodium arsenite solution. Wherein the reduction time is 2.0h and SO2The dosage is SO2The molar ratio of the arsenic to the arsenic is 2.10: 1, arsenic trioxide crystals which are saturated and separated out in the reduction process are dissolved into arsenous acid with the As content of 120g/L by using a sodium hydroxide solutionThe sodium solution is returned to the arsenic salt purification process in the zinc hydrometallurgy to be used as an arsenic raw material.
C. Acid leaching: and B, performing secondary leaching on the alkaline leaching residue obtained in the step A, wherein the temperature of the first-stage low-acid leaching is 60 ℃, the leaching time is 75 minutes, the pH of the low-acid leaching control end point is =2.2, the Cu ion concentration of the obtained low-acid leaching solution is 90g/L, the low-acid leaching residue enters the second-stage high-acid leaching, the liquid-solid ratio is 10:1, the temperature is 82 ℃, the time is 4 hours, 15mL of hydrogen peroxide is added into each liter of solution when the end point is approached, and the acidity of the high-acid leaching solution is 25 g/L.
D. Purifying and removing arsenic: and D, performing copper powder arsenic removal on the low-acid leaching solution obtained in the step C at the temperature of 85 ℃ for 4 hours, controlling the using amount of activated copper powder to be 4g/L and the granularity to be 220 meshes, and filtering to obtain arsenic removal solution and arsenic removal slag.
E. Controlling potential to deposit copper: d, carrying out potential-controlled copper deposition on the arsenic-removing liquid obtained in the step D, wherein the copper deposition zinc powder is 0.99 time of the theoretical amount required for copper replacement, the temperature is 60 ℃, the time is 80 minutes, the end point pH =4.0, the end point potential is 90mv, and the copper content in the copper deposition liquid is 0.30 g/L; the copper powder obtained by filtering is firstly pickled by sulfuric acid solution with 25g/L of sulfuric acid, the temperature is 55 ℃, the time is 80 minutes, and the liquid-solid ratio is 6: 1; washing the copper powder by deionized water for 2 times at 50 ℃ for 35 minutes at a liquid-solid ratio of 6:1, and carrying out vacuum drying treatment on the washed copper powder; and ball-milling the dried copper powder under the kerosene protection condition to obtain the superfine copper powder product.
F. And (3) oxidizing and precipitating cobalt: and E, adding sodium hypochlorite into the copper-removed solution obtained in the step E for carrying out oxidation cobalt precipitation, wherein the amount of the sodium hypochlorite is 13 times of the theoretical amount of oxidizing divalent cobalt into trivalent cobalt, the temperature is 80 ℃, the time is 75min, and the end point pH = 4.0.
Through comprehensive recovery of cobalt-nickel slag resources, a sodium arsenite solution, superfine copper powder, high-acid leaching slag and the like are respectively obtained, and the recovery rates of arsenic, copper, zinc, cobalt, lead and silver are respectively 96%, 98.6%, 97.2%, 95%, 99% and 99%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A resource comprehensive utilization method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt is characterized by comprising the following steps:
A. high-pressure alkaline arsenic leaching: leaching the slag of purifying cobalt and nickel by using the zinc hydrometallurgy arsenate under the condition that the alkali concentration is 3.8-5.2mol/L, wherein the leaching temperature is 125-;
B. and (3) arsenic reduction: cooling and crystallizing the alkaline leaching solution obtained in the step A to obtain sodium arsenate crystals, dissolving the sodium arsenate crystals by using water to obtain a sodium arsenate solution, adjusting the pH value of the sodium arsenate solution to 2-4, and introducing SO2Reducing to obtain a sodium arsenite solution; wherein the reduction time is 1.5-3.0h, SO2The dosage is SO2The molar ratio of the arsenic in the sodium arsenate solution to the arsenic (2.05-2.15) is 1;
C. acid leaching: b, carrying out secondary leaching on the alkaline leaching residue obtained in the step A, wherein a leaching agent is a sulfuric acid solution: the first stage of low acid leaching, wherein the sulfuric acid concentration of the low acid leaching solution is 15-25 g/L, the leaching temperature is 55-65 ℃, the leaching time is 60-90min, the pH of the low acid leaching control end point is 1.5-2.8, the obtained low acid leaching solution has the Cu ion concentration of 80-95g/L, and the low acid leaching slag enters the second stage of high acid leaching; in the second stage of peracid leaching, the sulfuric acid concentration of a peracid leaching solution is 60g/L-90g/L, the liquid-solid ratio is (8-12): 1, the leaching temperature is 80-85 ℃, the leaching time is 3-5h, the sulfuric acid content at the end of leaching is 15-30g/L, and 10-20mL of hydrogen peroxide is added to each liter of solution when the end point is approached;
D. purifying and removing arsenic: c, adding copper powder into the low-acid leaching solution obtained in the step C, removing arsenic from the copper powder at the temperature of 82-88 ℃ for 3-5h, wherein the amount of the copper powder is 3-5g of copper powder added into each liter of low-acid leaching solution, and filtering to obtain arsenic-removed liquid and arsenic-removed slag;
E. controlling potential to deposit copper: d, carrying out potential-controlled copper deposition on the arsenic-removing liquid obtained in the step D, wherein the copper deposition temperature is 55-65 ℃, the copper deposition time is 60-90min, the end point pH =3.2-4.5, and the end point potential is 80-100 mV, and filtering to obtain a copper deposition liquid and copper powder;
F. and (3) oxidizing and precipitating cobalt: and D, adding sodium hypochlorite into the copper-removed liquid obtained in the step E for carrying out oxidation cobalt precipitation at the temperature of 75-85 ℃ for 60-90min, wherein the end point pH = 3.5-5.0.
2. The method for comprehensively utilizing resources of cobalt-nickel slag purified by zinc hydrometallurgy arsenate according to claim 1, characterized by comprising the following steps: in the step B, the acid used for adjusting the pH value of the sodium arsenate solution is sulfuric acid, the arsenic trioxide crystals which are saturated and separated out in the reduction process are dissolved by using a sodium hydroxide solution to obtain a 130g/L As-containing 100-plus sodium arsenite solution, and zinc is refined by a wet method to be used for purifying arsenic salt and removing cobalt.
3. The method for comprehensively utilizing resources of cobalt-nickel slag purified by zinc hydrometallurgy arsenate according to claim 1, characterized by comprising the following steps: the copper powder in the step D is activated copper powder, and the granularity is controlled to be 180-260 meshes.
4. The method for comprehensively utilizing resources of cobalt-nickel slag purified by zinc hydrometallurgy arsenate according to claim 1, characterized by comprising the following steps: the copper precipitation zinc powder in the step E is 0.98-1.0 time of the theoretical amount required by copper replacement, Zn in the used zinc powder is more than or equal to 99.9%, and the granularity of the zinc powder is 0.25-0.09 mm; the copper content in the solution after copper precipitation is 0.23-0.32 g/L.
5. The comprehensive resource utilization method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt according to claim 1 or 4, characterized in that: and E, controlling the potential to precipitate copper to obtain copper powder, pickling the copper powder by using a sulfuric acid solution containing 20-30g/L sulfuric acid, washing and drying the copper powder by using deionized water, and ball-milling the obtained copper powder under a protection condition to obtain superfine copper powder.
6. The method for comprehensively utilizing resources of cobalt-nickel slag purified by zinc hydrometallurgy arsenate according to claim 1, characterized by comprising the following steps: and F, enabling free alkali in the sodium hypochlorite to be 0.1-0.5%, enabling the mass concentration of effective chlorine to be 5-11%, and enabling the amount of the required sodium hypochlorite to be 12-15 times of the theoretical molar amount of the divalent cobalt oxide to be trivalent cobalt.
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| CN113122735B (en) * | 2021-04-02 | 2022-11-15 | 云南云铜锌业股份有限公司 | Alkali-process zinc powder combined smelting method |
| CN113151689A (en) * | 2021-04-16 | 2021-07-23 | 内蒙古兴安铜锌冶炼有限公司 | Method for enriching cobalt in zinc hydrometallurgy zinc powder and antimonate purification slag |
| CN113462894A (en) * | 2021-06-03 | 2021-10-01 | 甘肃康兴科技有限公司 | Device and method for recovering nickel, copper and cobalt from nickel smelting water-quenched slag |
| CN114182095A (en) * | 2021-09-18 | 2022-03-15 | 云南云铜锌业股份有限公司 | Method for recovering cobalt from zinc, cobalt and nickel slag purified by zinc hydrometallurgy |
| CN115491496B (en) * | 2022-09-22 | 2024-01-16 | 郑州大学 | Method for selectively separating cobalt, manganese, zinc and cadmium from purified cobalt slag of zinc hydrometallurgy |
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| CN102162032B (en) * | 2011-03-14 | 2013-01-02 | 云南罗平锌电股份有限公司 | Method for recovering lead and silver from purification slag of zinc hydrometallurgy |
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